EP3099698B1 - Silanmodifizierte formamide - Google Patents

Silanmodifizierte formamide Download PDF

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Publication number
EP3099698B1
EP3099698B1 EP15702206.2A EP15702206A EP3099698B1 EP 3099698 B1 EP3099698 B1 EP 3099698B1 EP 15702206 A EP15702206 A EP 15702206A EP 3099698 B1 EP3099698 B1 EP 3099698B1
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EP
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Prior art keywords
reactive
formula
wood
materials
isocyanate
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EP15702206.2A
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German (de)
English (en)
French (fr)
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EP3099698A1 (de
Inventor
Christoph Eggert
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Covestro Deutschland AG
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Covestro Deutschland AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1888—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of other Si-linkages, e.g. Si-N
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
    • C08G18/8019—Masked aromatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/16—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • the present invention relates to novel silane-modified formamide prepolymers of the formula (I) for coating, bonding and / or sealing various substrate materials, such as e.g. Metal, wood, glass and / or plastic.
  • a reactive one-component adhesive system comprising the silane-modified formamide prepolymers of the formula (I) according to the invention is provided.
  • Silane-modified polymers have been known for years in general, and sealants based on silane-modified prepolymers or polymers have proven useful for a wide variety of applications, for example in seam sealing in vehicle construction, in windows or in facade construction.
  • silane-modified polymers are polymers containing silane groups having hydrolyzable groups and whose polymer backbone is not essentially composed of O-Si-O-Si chains, as is the case with silicones but CC chains which in most cases are interrupted by heteroatoms and further contain urethane, ether, ester, urea, amide and other structural units.
  • the radicals on the silane groups for example usually acetate or alkoxy groups, are hydrolyzed to form reactive silanols, which subsequently condense and harden to form a high molecular weight network with elimination of water, alcohol or acetic acid.
  • silane-modified polymers lies essentially in their particular property profile.
  • coatings, adhesives or sealants containing silane-modified polymers are distinguished by high adhesion to a wide variety of substrates without the need for extensive pretreatment (no primer required). This is because on inorganic substrate surfaces normally OH groups are present which can react with the reactive silanols of the polymer which are formed under the action of moisture.
  • the properties of the silane-modified polymers can be adapted to a wide variety of applications.
  • a disadvantage of coating, adhesives and sealants based on silane-modified polyureas lies in the high viscosity of their prepolymers. Due to the high viscosity, the use of silane-modified polyureas is only possible to a limited extent since the coating or sealants to be used normally have to be applied in a liquid to pasty manner to the substrate parts to be coated or bonded. Consequently, a too viscous prepolymer makes it difficult or impossible to use it as a coating, adhesive and / or sealant.
  • the degree of hardness of the resulting coating, bonding and / or seal as the final product after the silane crosslinking for the particular application is crucial.
  • end products with a high degree of hardness are usually present.
  • silane-modified polyurethanes provide softer end products after cure.
  • the synthesis of silane-modified high silane polyurethanes is difficult to implement because of the relatively expensive NCO-functionalized silane precursors.
  • the monomeric NCO content in silane-modified polymers plays a decisive role in this context: because of the not insignificant vapor pressure of the isocyanates (even at room temperature), isocyanate vapors which can be injurious to health or at least sensitizing can already occur during spray application. Consequently, the development of reactive prepolymers that are substantially free of isocyanate monomers and at least below the Total Reactive Isocyanate Group (TRIG) concentration in accordance with the Technical Standard for Hazardous Substances (TRGS) 430 (Issue 3/2009) of 0.018 mg / m 3 NCO, preferably below 0.01 mg / m 3 , more preferably below 0.001 mg / m 3 , desirable.
  • TAG Total Reactive Isocyanate Group
  • a reactive one-component adhesive system which is easier to handle due to lower viscosity and lower crystallinity and at the same time allows high chemical stability of the final products.
  • the aim is to produce polymer end products which can be produced cost-effectively with an advantageous balance of properties, in particular degree of curing and chemical stability.
  • the present invention relates to compounds of formula (I) according to claim 1, which is a one-component adhesive system / coating system for improved coating, bonding and / or sealing of various substrate materials, such as. Metal, wood, glass and / or plastic, are suitable.
  • the invention When finally cured, the invention provides condensed polymers via Si-O-Si bridges as permanent coatings, adhesives and / or sealants.
  • the present invention provides processes for the preparation of the compounds of formula (I).
  • a process for the preparation of the compound of the formula (I) comprising reacting the silane-modified formamide of the formula (Ia) with the isocyanate of the formula Y- (NCO) m : wherein Y, R 1 , R 2 , R 3 , n and m are as defined in claim 1.
  • a reactive, one-component adhesive and / or coating system comprising at least one compound of the formula (I) is provided.
  • the compound of the formula (I) is used for the production of adhesives and sealants, paints, coatings, sizes, inks and / or printing inks.
  • a composite body is disclosed according to the invention, which is connected by the one-component adhesive system according to the invention.
  • alicyclic is intended to mean carbocyclic or heterocyclic compounds which do not belong to the aromatic compounds, such as cycloalkanes, cycloalkenes or oxa-, thia-, aza- or thiazacycloalkanes. Specific examples thereof include cyclohexyl groups, cyclopentyl groups, and their derivatives interrupted by one or two N or O atoms, e.g. Pyrimidine, pyrazine, tetrahydropyran or tetrahydrofuran.
  • the term "araliphatic” shall mean substituted by aryl groups alkyl radicals, such as. Benzyl, phenylethyl, biphenyl, etc.
  • it is a substitution by halogen (especially -F, -Cl), C 1-6 alkoxy (especially methoxy and
  • low molecular weight is intended to mean compounds whose molecular weight does not exceed about 800 g.mol -1 .
  • high molecular weight is intended to mean compounds whose molecular weight exceeds about 800 g.mol -1 .
  • the term "monoisocyanate” is intended to mean a compound represented by A-NCO, wherein A represents an aromatic, araliphatic, aliphatic or cycloaliphatic group having from 6 to 50 carbon atoms.
  • polyisocyanate for aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates having an NCO functionality of preferably> 2, in particular di- and triisocyanates.
  • the term "monomer” is intended to mean a low molecular weight compound having functional groups involved in the construction of oligomers and / or (pre-) polymers and having a defined molecular weight.
  • oligomer is intended to mean a compound in which only a few monomers of the same or different type are repeatedly linked together.
  • prepolymer is intended to mean oligomeric compounds having functional groups involved in the final construction of polymers.
  • polymer is intended to mean high molecular weight compounds in which monomers, oligomers and / or prepolymers of the same or different types are repeatedly linked to one another and which may differ with regard to the degree of polymerization, molecular weight distribution or chain length.
  • the structural unit Y is a radical derived from a monoisocyanate.
  • monoisocyanates are hexyl isocyanate, 6-chloro-hexyl isocyanate, n-octyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, 2,3,4-methylcyclohexyl isocyanate, 3,3,5-trimethylcyclohexyl isocyanate, 2-norbornyl-methyl isocyanate, decyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate , Hexadecyl isocyanate, octadecyl isocyanate, 3-butoxypropyl isocyanate, 3- (2-ethylhexyloxy) propyl isocyanate, phenyl isocyanate, tolyl isocyanates, chlorophen
  • 4-dodecylphenyl isocyanate 4-cyclohexylphenyl isocyanate, 1-naphthyl isocyanate, isocyanatoamides of 1 mole of diisocyanates and 1 mole of monocarboxylic acids, preferably from tolylene diisocyanates, diphenylmethane diisocyanates and hexamethylene diisocyanate with aliphatic monocarboxylic acids having preferably at least 6 C atoms, eg (6-isocyanatohexyl) -stearic acid amide, (3-isocyanatotolyl) -stearic acid amide, (6-isocyanatohexyl) benzamide, each alone or in admixture with several monoisocyanates.
  • the structural unit Y is a radical derived from a polyisocyanate.
  • Suitable polyisocyanates which are known to those skilled in the aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates of an NCO functionality of preferably ⁇ 2 use. These may also have iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acylurea and / or carbodiimide structures.
  • polyisocyanates are based on those skilled in the art known di- or triisocyanates with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups, it is irrelevant whether they are using phosgene or were prepared by phosgene-free method.
  • di- or triisocyanates examples include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2- dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4- Bis (isocyanatomethyl) cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane (Desmodur® W, Bayer AG, Le
  • the polyisocyanates particularly preferably have an average NCO functionality of from 2.0 to 5.0, very particularly preferably from 2.3 to 4.5, and preferably a content of isocyanate groups of from 5.0 to 27.0% by weight, particularly preferably from 14.0 to 24.0% by weight and preferably a content of monomeric diisocyanates of less than 1% by weight, more preferably less than 0.5% by weight.
  • the polyisocyanates of the abovementioned type are particularly preferably based on hexamethylene diisocyanate, isophorone diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes, TDI, MDI, and mixtures thereof.
  • Suitable polyols which may be used are all polyols known per se to the person skilled in polyurethane chemistry, which preferably have an average OH functionality ⁇ 1.5, particularly preferably from 1.8 to 2.5.
  • polystyrene resin examples include 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol, 2,2,4-trimethylpentanediol), triols (eg glycerol, trimethylolpropane) and tetraols ( eg pentaerythritol), polyether polyols, polyester polyols, polyacrylate polyols and polycarbonate polyols.
  • Preferred polyols are polyether-based substances of the aforementioned type.
  • polyether polyols When polyether polyols are used, polyether polyols having a number-average molecular weight Mn of preferably 300 to 20 000 g / mol, more preferably 1000 to 12000 g / mol, very particularly preferably 2000 to 6000 g / mol are used.
  • they preferably have an average OH functionality of ⁇ 1.9, more preferably> 1.95.
  • the OH functionality of these polyethers is preferably ⁇ 6, particularly preferably ⁇ 4, very particularly preferably ⁇ 2.2.
  • suitable polyols are polyester polyols from the condensation reaction of suitable alcohols and acids.
  • Alcohols here are primary and diprimary diols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol or neopentyl glycol, and also higher-value alcohols, such as trimethylolpropane , Trimethylolethane or pentaerythritol application.
  • Suitable condensation partners are acid components such as adipic acid or phthalic acids.
  • polyesterpolyols can be determined by the number of caprolactone units used.
  • the preferred molecular weight of the polyester polyols (number average) is ⁇ 1000 g / mol.
  • the preferred functionality of the polyester polyols is 2 to 3.
  • Polyacrylate polyols are also suitable for the preparation of the prepolymers of the invention.
  • the polyacrylate polyols have a number average molecular weight of from 200 to 10,000 g / mol, more preferably from 200 to 6,000 g / mol, and most preferably from 200 to 2,500 g / mol.
  • the functionality of the polyacrylate polyols used is preferably 1.6 to 3.8, more preferably 1.8 to 3.5.
  • the OH number of these polyacrylate polyols is preferably 15 to 150, more preferably 20 to 100 and most preferably 40 to 80 mg KOH / g.
  • Suitable examples Acryflow ® P60 and P90 commercial products from. Lyondell, US).
  • Aliphatic polycarbonate polyols are also suitable for the construction of the prepolymers of the invention.
  • Polycarbonate polyols can be known from the condensation reaction of phosgene with polyols or the transesterification of suitable organic carbonates with polyols.
  • Suitable organic carbonates are aryl-alkyl-alkylene carbonates and mixtures thereof. Examples which may be mentioned are diphenyl carbonate (DPC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethylene carbonate.
  • Suitable polyols are those mentioned above under the section Polyesterpolyols into consideration.
  • the functionality of the polycarbonate polyols used is preferably 1.6 to 3.8, more preferably 1.8 to 3.5.
  • polycarbonate polyols have a number average molecular weight of preferably 100 to 6000 g / mol and more preferably from 100 to 4000 g / mol.
  • the OH number is dependent on the functionality of the polycarbonate polyols and is typically 20 to 900 mg KOH / g.
  • polystyrene resin examples include those in EP-A 0 689 556 and EP-A 0 937 110 described, z.
  • Hydroxyl-containing polybutadienes can also serve as polyols.
  • the production of the polyurethane prepolymers Y- (NCO) m according to the invention is basically carried out in a manner known from polyurethane chemistry.
  • the polyols (individually or as a mixture) are reacted with an excess of the polyisocyanate (individually or as a mixture) optionally in the presence of a catalyst and / or of auxiliaries and additives.
  • the homogeneous reaction mixture is stirred until a constant NCO value is obtained.
  • optionally unreacted polyisocyanate can be removed by continuous distillation.
  • a continuous distillation process in the sense of the invention is understood to mean a process in which only a respective subset of the prepolymer from the previously described process step is briefly exposed to an elevated temperature, while the amount not yet in the distillation process remains at a significantly lower temperature.
  • elevated temperature is to be understood as meaning the evaporation of the volatile constituents at a correspondingly selected pressure.
  • the distillation at a temperature of less than 170 ° C, more preferably 110 to 170 ° C, most preferably 125 to 145 ° C and at pressures of less than 20 mbar, more preferably less than 10 mbar, most preferably at 0.05 to 5 mbar.
  • the temperature of the prepolymer-containing reaction mixture not yet in the distillation process is preferably 0 to 60 ° C., particularly preferably 15 to 40 ° C. and very particularly preferably 20 to 40 ° C.
  • the temperature difference between the distillation temperature and the temperature of the not yet in the distillation process amount of the prepolymer-containing reaction mixture is at least 5 ° C, more preferably at least 15 ° C, most preferably 15 to 40 ° C.
  • the distillation is conducted at such a rate that a volume increment of the prepolymer-containing reaction mixture to be distilled is exposed to the distillation temperature for less than 10 minutes, more preferably less than 5 minutes and then optionally brought back to the starting temperature of the prepolymer-containing reaction mixture prior to distillation by active cooling ,
  • the temperature load that is passed through is preferably such that the temperature of the reaction mixture before distillation or of the prepolymer after distillation is higher than the distillation temperature used at least 5 ° C., particularly preferably at least 15 ° C., very particularly preferably 15 to 40 ° C.
  • Preferred continuous distillation techniques are short path, falling film and / or thin film distillation (see for example Chemical Engineering, Wiley-VCH, Vol. 1, 5th Ed., Pp. 333-334 ).
  • Falling film evaporators consist of a standing bundle of long tubes, in which the liquid to be evaporated is placed on top and flows down as a film. In the shell room, the heating is done by steam. In the pipes, vapor bubbles form, which flow down with the liquid and provide turbulent conditions. Steam and liquid separate at the bottom in a separation vessel.
  • Thin-film evaporators are suitable apparatus for the evaporation of temperature-sensitive substances, which may only be thermally stressed for a short time.
  • the liquid to be evaporated is placed on top in a tube with jacket heating. She is streaming down there as a movie. Inside the tube, a wiper suspended from a shaft rotates to provide a constant film thickness.
  • the continuous distillation technique used is preferably thin film distillation with the abovementioned parameters.
  • the equivalent ratio of the NCO groups of the polyisocyanate to the OH groups of the polyol in the reaction is preferably 10: 1 to 2: 1, more preferably 7: 1 to 2: 1.
  • the reaction temperature chosen is 0 ° C. to 250 ° C., preferably 20 ° C. to 140 ° C., very particularly preferably 40 ° C. to 100 ° C.
  • process according to the invention can also be carried out in the presence of solvents such as aromatics, chlorinated aromatics, esters or chlorinated hydrocarbons.
  • catalysts such as organometallic compounds, amines (e.g., tertiary amines) or metal compounds such as lead octoate, mercury succinate, zinc triflate, tin octoate or dibutyltin dilaurate can be used. If catalysts are used, they are preferably added in amounts of 0.001 to 5 wt .-%, in particular 0.002 to 2 wt .-%, based on the total amount of the polyisocyanates to be reacted and polyols.
  • the compounds of the formula (I) according to the invention are suitable as binders for coating, adhesives and / or sealants.
  • the compounds of formula (I) according to the invention have (at 23 ° C) viscosities in the range of 100 to 1,000,000 mPa ⁇ s, preferably 1,000 to 500,000 mPa ⁇ s, more preferably 5,000 to 300,000 mPa ⁇ s.
  • the compounds of formula (I) according to the invention are due to the present acyl urea group lower in their viscosity compared to the analogous products having a urea group. This leads, as known in the art, to improved handling and / or further processing to pigmented coatings or better incorporation of fillers, such as e.g. Chalks for the formulation of adhesives or sealants.
  • the compounds of the formula (I) according to the invention can be prepared by the following two-stage process:
  • an excess of the alkyl formate R'O-CHO is preferably added dropwise to the amine H 2 NR 1 -Si (R 2 ) n (OR 3 ) 3-n , wherein R 'is preferably an alkyl group having 1 to 4 carbon atoms.
  • R ' is preferably an alkyl group having 1 to 4 carbon atoms.
  • 1 mol of amine is reacted with an excess of 1.01 to 6 moles of alkyl formate R'O-CHO, particularly preferably 1.05 to 4 mol, at the boiling point of the alkyl formate.
  • the excess formic acid R'O-CHO and the resulting alcohol R'-OH is distilled off by means of thin-layer distillation and the resulting product (Ia) optionally filtered off.
  • the preparation of the compounds of the formula (I) can be carried out without the use of catalysts.
  • catalysts can be added to speed up the reaction.
  • tert. Amines such as Triethylamine, tributylamine, dimethylbenzylamine, diethylbenzylamine, pyridine, methylpyridine, dicyclohexylmethylamine, dimethylcyclohexylamine, N, N, N ', N'-tetramethyldiaminodiethylether, bis (dimethylaminopropyl) urea, N-methyl- or N-ethylmorpholine, N-cocomorpholine, N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-1,3-butanediamine, N, N, N ', N'-tetramethyl- 1,6-hexanediamine,
  • 1,5-diazabicyclo [4.3.0] nonene DBN
  • 1,8-diazabicyclo (5.4.0) undecene-7 DBU
  • 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine alkanolamine compounds, such as.
  • Triethanolamine triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, dimethylaminoethanol and 2- (N, N-dimethylaminoethoxy) ethanol, N, N ', N "-tris- (dialkylaminoalkyl) hexahydrotriazines such as N, N ', N "-Tris- (dimethylaminopropyl) -s-hexa-hydrotriazine, bis (dimethylaminoethyl) ethers and metal salts, such as.
  • iron (II) chloride iron (III) chloride, bismuth (III) -2-ethyl hexanoate, bismuth (III) octoate, bismuth (III) neodecanoate, zinc chloride, zinc 2-ethylcaproate, zinc (II) trifluoromethanesulfonate (zinc triflate), stannous octoate, stannous (ethyl) caproate, tin ( II) -palmitate, dibutyltin (IV) dilaurate (DBTL), dibutyltin (IV) dichloride or lead octoate used.
  • iron (II) chloride iron (III) chloride, bismuth (III) -2-ethyl hexanoate, bismuth (III) octoate, bismuth (III) neodecanoate
  • zinc chloride zinc 2-ethylcaproate
  • Preferred catalysts to be used are tertiary amines, amidines and tin compounds or zinc compounds of the type mentioned.
  • Particularly preferred catalysts are 1,4-diazabicyclo- (2,2,2) -octane (DABCO), 1,5-diazabicyclo [4.3.0] nonen (DBN), 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) and dibutyltin (IV) dilaurate (DBTL) and zinc (II) trifluoromethanesulfonate (zinc triflate).
  • the above-exemplified catalysts can be used in the reaction individually or in the form of any mixtures and come here, if at all, in amounts of 0.001 to 1.0 wt .-%, preferably 0.01 to 0.5 wt .-%, calculated as the total amount of catalysts used, based on the total amount of the starting compounds used.
  • the course of the implementation can be achieved by z. B. titrimetric determination of the NCO content be followed. After reaching the desired NCO content, the reaction is stopped.
  • the compounds of the formula (I) prepared in this way are clear, virtually colorless products which, depending on the starting materials chosen, are low to highly viscous liquids and residual contents of monomeric starting diisocyanates of less than 1.0% by weight, preferably less than 0 , 5 wt .-%, more preferably less than 0.3 wt .-%, based on the total mass of the reaction product having.
  • Any still detectable NCO residual contents can be intercepted by the addition of methanol.
  • water scavengers may be advantageous.
  • ortho-formic esters such as. B. triethyl orthoformate
  • vinylsilanes such as. As vinyltrimethoxysilane
  • organic phosphates such as. As dibutyl phosphate used become.
  • the water scavengers are used in amounts of up to 5% by weight, preferably up to 2% by weight, based on the total amount of the starting materials.
  • catalysts and / or water scavengers are used, they can be added to the starting compounds before the actual reaction has begun. But it is also possible to add these aids to the reaction mixture at any time during the reaction.
  • the processes described here take place under a protective gas atmosphere, such as nitrogen.
  • silane-modified polymers of the formula (I) disclosed herein can be used according to the invention for the production of adhesives and sealants, paints, coatings, sizes, inks and / or printing inks.
  • the advantage of this process is that the properties of the silane-modified polymers of the formula (I) can be adapted to a large number of very different applications via the structures of the formula Y- (NCO) m used.
  • the compounds of the formula (I) are used for a reactive one-component adhesive system.
  • the reactive one-component adhesive system is characterized in that it contains at least one compound of the formula (I).
  • catalysts which accelerate the hydrolysis and condensation of the silanol groups.
  • Such catalysts are known to a person skilled in the art.
  • acids such as.
  • sulfuric acid such as.
  • p-toluenesulfonic acid such as, sulfuric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid and dibutyl phosphate
  • bases such as N-substituted amidines such as 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) and 1,5-diazabicyclo [5.4.0] undec-7-ene (DBU), but also Metal salts and chelates, such as.
  • DBN 1,5-diazabicyclo [4.3.0] non-5-ene
  • DBU 1,5-diazabicyclo [5.4.0] undec-7-ene
  • Metal salts and chelates such as.
  • tetraisopropyl titanate tetrabutyl titanate
  • titanium (IV) acetylacetonate aluminum tri-sec-butylate
  • aluminum acetylacetonate aluminum triflate or tin triflate
  • catalysts are used, if at all, in amounts of up to 5% by weight, preferably up to 2% by weight, based on the weight of the silane-modified prepolymers used.
  • the curing of the one-component adhesive system formulated from the compounds of the formula (I) according to the invention over a wide temperature range for example from -20 to 200 ° C, preferably from 0 to 180 ° C, especially preferably from 20 to 160 ° C, take place.
  • any other hydrolyzable silane compounds such as. B. tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, (3-glycidyloxypropyl) -methyldiethoxysilane, (3-glycidyloxypropyl) trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane or silane-functional copolymers described in the US 4,499,150 mentioned type, or mixtures of such silane compounds are added as reactants.
  • the reactive one-part adhesive system of the invention may optionally contain other additives and / or adjuvants known in the art.
  • additives for pigments, antioxidants, water scavengers, fillers, slip additives, flow control agents, rheology additives, foam stabilizers, water repellents, air entraining agents, adhesive-enhancing additives (adhesion promoters), compounding agents, plasticizers, aging inhibitors, flame retardants and / or UV stabilizers to name.
  • suitable fillers are carbon black, precipitated silicas, pyrogenic silicic acids, mineral chalks and precipitation precipitates.
  • suitable plasticizers include phthalic acid esters, adipic acid esters, alkylsulfonic acid esters of phenol, phosphoric esters or else relatively high molecular weight polypropylene glycols.
  • Particularly suitable water scavengers are alkoxysilyl compounds such as vinyltrimethoxysilane, methyltrimethoxysilane, i-butyltrimethoxysilane, hexadecyltrimethoxysilane.
  • Adhesion promoters used are the known functional silanes, for example aminosilanes of the abovementioned type, but also N-aminoethyl-3-aminopropyltrimethoxy and / or N-aminoethyl-3-aminopropylmethyldimethoxysilane, epoxysilanes and / or mercaptosilanes.
  • the compounds of the formula (I) according to the invention can also be admixed to conventional one-component and / or two-component polyurethane adhesive systems, for example as an additive.
  • inventive reactive one-component adhesive system as described above, previously applied to the substrates to be bonded, comes through the above-described networking permanent bonding or sealing of the substrates to conditions.
  • a primer or a primer composition is advantageous, but not absolutely necessary according to the invention. It can therefore be omitted in one embodiment.
  • Suitable substrates which are suitable for bonding and / or sealing via the reactive, one-component reactive adhesive system according to the invention are metals, glass, wood, concrete, stone, ceramic, textile and / or plastics.
  • the substrates to be bonded may be the same or different.
  • the reactive, one-component adhesive system according to the invention is used for the bonding and / or sealing of metals, glass and / or plastics.
  • Suitable metal substrates can generally be made from any metal or metal alloy common in the art. Preferably, metals such as aluminum, stainless steel, steel, titanium, ferrous metals and alloys are used. The substrates to be bonded may also be composed of different metals.
  • the plastic substrates to be bonded are, for example, polycarbonates (PC), polyamides, polyvinyl chloride, polyurethanes, polyvinyl acetate, polyacrylates or polymethacrylates, polyethylene, polystyrene, polypropylene and / or polyesters, such as e.g. Polybutylene terephthalate (PBT) and / or polyethylene terephthalate (PET).
  • PC polycarbonates
  • PC polyamides
  • polyvinyl chloride polyurethanes
  • polyvinyl acetate polyacrylates or polymethacrylates
  • polyethylene polystyrene
  • polypropylene polypropylene and / or polyesters
  • polyesters such as e.g. Polybutylene terephthalate (PBT) and / or polyethylene terephthalate (PET).
  • the substrates can also be painted or printed.
  • the substrates to be bonded can have any shape that is necessary for the particular application of the resulting composite body.
  • the substrates are flat.
  • the NCO contents were determined titrimetrically in accordance with DIN EN ISO 11909.
  • the residual monomer contents were measured according to DIN EN ISO 10283 by gas chromatography with an internal standard.
  • N- (3-trimethoxysilylpropyl) formamide from Example 1 are subsequently metered in and the reaction mixture is stirred at 80 ° C. until an isocyanate content can no longer be determined titrimetrically.
  • To stabilize the resulting silane-terminated prepolymer 32 mg of dibutyl phosphate and 2.14 g of vinyltrimethoxysilane are added as a water scavenger.
  • the resulting binder is a clear colorless mass and has a viscosity of 21,000 mPa.s at 23 ° C.
  • Example 6 (Comparative Example to Example 5)
  • the binder is adjusted to a solids content of 50% with butyl acetate and 0.25% Lupragen N 700 (1,8-diazabicyclo-5,4,0-undecene-7) BASF added and on glass plates with a layer thickness (wet) of 50 microns gerakelt. After a drying time of 4 h at 23 ° C and a relative humidity of 50%, the coating is dry to the touch and shows after 4 days good solvent resistance to xylene, 1-Methoxypropylacetat-2, ethyl acetate and acetone.
  • the binder is adjusted to a solids content of 50% with ethyl acetate and 0.25% Lupragen ® N 700 (1,8-diazabicyclo-5,4,0-undecene-7) BASF SE added and on glass plates with a layer thickness (wet) of 50 microns gerakelt. After a drying time of 4 h at 23 ° C and a relative humidity of 50%, the coating is dry to the touch and shows after 4 days good solvent resistance to xylene, 1-Methoxypropylacetat-2, ethyl acetate and acetone.
  • the binder with 0.25% Lupragen ® N 700 is added (1,8-diazabicyclo-5,4,0-undecene-7) from BASF SE, and knife-coated onto glass plates with a layer thickness (wet) of 50 .mu.m. After a drying time of 4h at 23 ° C and a relative humidity of 50%, the coating is dry to the touch and shows after 4 days good solvent resistance to xylene, 1-Methoxypropylacetat-2, ethyl acetate and acetone.
  • Example 10 (Comparative Example to Example 9)
  • the binder with filler (® Socal U1S2 Fa. Solvay), added plasticizer (Jayflex TM DINP Fa. Exxon) and desiccant (Dynasylan ® VTMO Fa. Evonik) and in a vacuum with wall scraper at 3000 U / min mixed.
  • the adhesion promoter is (Dynasylan ® 1146 of Fa. Evonik) were added and stirred in within 5 min at 1000 U / min.
  • the catalyst (Lupragen ® N700 Fa. BASF SE) is stirred at 1000 U / min and, finally, the finished mixture deaerated under vacuum.
  • both membranes of 2 mm thickness, as well as specimens on glass substrate according to DIN EN ISO 11600 are produced.
  • the shore hardness test is carried out on the membranes in accordance with DIN 53505.
  • the modulus at 50% elongation is measured at 23 ° C. in accordance with DIN EN ISO 11600.
  • Example 15 (prepolymer from Ex. 9) Shore A hardness 52 50% modulus [N / mm 2 ] 2.4 Film drying time, 100 ⁇ m [min] 150 Elongation at break [%] 64.6

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
EP15702206.2A 2014-01-31 2015-01-26 Silanmodifizierte formamide Not-in-force EP3099698B1 (de)

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EP3085718B1 (de) 2015-04-21 2024-04-17 Covestro Deutschland AG Polyisocyanuratkunststoff enthaltend siloxangruppen und verfahren zu dessen herstellung
EP3298058B1 (de) 2015-05-21 2019-04-17 Covestro Deutschland AG Polyurethan-beschichtungszusammensetzungen
JP2022505990A (ja) 2018-10-30 2022-01-14 コベストロ・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・アンド・コー・カーゲー 層接着が改善された複層ペイント構造
WO2020089019A1 (de) 2018-10-30 2020-05-07 Covestro Deutschland Ag Verfahren zur herstellung eines mehrschicht-lackaufbaus mit einer deckschicht aus silangruppen-enthaltenden prepolymeren
CN112812680A (zh) * 2021-01-26 2021-05-18 广东爱上体育产业股份有限公司 一种强渗透型提升水泥混凝土强度的密封底漆及其制备方法

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US4499150A (en) 1983-03-29 1985-02-12 Ppg Industries, Inc. Color plus clear coating method utilizing addition interpolymers containing alkoxy silane and/or acyloxy silane groups
DE3524215A1 (de) 1985-07-06 1987-01-08 Degussa N-silylpropyl-n'-acyl-harnstoffe und verfahren zur herstellung
DE4308097A1 (de) 1993-03-15 1994-09-22 Henkel Kgaa Polyol für ein Isocyanat-Gießharz und Beschichtungen
DE19646424A1 (de) 1996-11-11 1998-05-14 Henkel Kgaa Verwendung von Polyolen für Isocyanat-Gießharze und -Beschichtungsmassen
DE102007032666A1 (de) * 2007-07-13 2009-01-22 Bayer Materialscience Ag Allophanat- und Silangruppen enthaltende Polyisocyanate
US8058463B2 (en) * 2007-12-04 2011-11-15 E. I. Du Pont De Nemours And Compnay Fluorosilanes
DE102009033636A1 (de) * 2009-07-17 2011-01-20 Bayer Materialscience Ag Formamide enthaltende Reaktivsysteme
DE102009047964A1 (de) * 2009-10-01 2011-04-21 Bayer Materialscience Ag Hochfunktionelle Allophanat- und Silangruppen enthaltende Polyisocyanate

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JP6532473B2 (ja) 2019-06-19
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US10040808B2 (en) 2018-08-07
EP3099698A1 (de) 2016-12-07

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